TWI482837B - Complexes with tridentate ligands - Google Patents

Description

Complex with trigeminal ligand

The present invention relates to organic light-emitting devices (OLEDs), and more particularly to phosphorescent organic materials used in such devices. More specifically, the present invention relates to an emissive phosphorescent material comprising at least one tridentate ligand bonded to a metal center, wherein at least one of the tridentate ligands is bonded to a carbon-metal bond.

This application is a continuation-in-part of U.S. Patent Application Serial No. 11/973,265, filed on Oct. 4, 2007, which is incorporated herein by reference.

Optoelectronic devices utilizing organic materials have gradually become generally desirable for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, and thus organic optoelectronic devices have the potential to outweigh the cost benefits of inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, make them ideal for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which the organic emissive layer emits light can generally be readily adjusted with a suitable dopant.

The term "organic" as used herein includes polymeric materials as well as small molecular organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. Small molecules can contain repeating units in some cases. For example, the use of a long chain alkyl group as a substituent does not remove the molecule from the "small molecule" species. Small molecules can also be incorporated into the polymer, for example as a pendant group on the polymer backbone, or as part of the backbone. Small molecules can also act as a core part of the dendrimer, which contains a series of chemical shells that are built on the core moiety. The core portion of the dendrimer can be a fluorescent or phosphorescent small molecule emitter. The dendrites can be "small molecules" and all of the dendrimers currently used in the field of OLEDs are small molecules. In general, small molecules have well-defined chemical formulas with a single molecular weight, whereas polymers have chemical formulas and molecular weights that can vary with the molecule.

OLEDs utilize an organic film that emits light when a voltage is applied across the device. OLED systems are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting. A number of OLED materials and types are described in U.S. Patent Nos. 5,844,363, 6, 303, 238, and 5, 707, 745, the entireties of each of

OLED devices are typically, but not always, intended to emit light through at least one electrode, and one or more transparent electrodes can be used in an organic optoelectronic device. For example, a transparent electrode material, such as indium tin oxide (ITO), can be used as the bottom electrode. A transparent top electrode can also be used as disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, the entireties of each of For devices intended to emit light only through the bottom electrode, the top electrode need not be transparent and may comprise a thick and reflective metal layer with high electrical conductivity. Likewise, for devices intended to emit light only through the top electrode, the bottom electrode can be opaque and/or reflective. Where the electrodes do not have to be transparent, the use of thicker layers provides better conductivity, while the use of reflective electrodes increases the amount of light that is emitted through the other electrodes by reflecting the light back toward the transparent electrodes. It is also possible to manufacture a completely transparent device in which both electrodes are transparent. Side-emitting OLEDs can also be fabricated, and one or both of the electrodes can be opaque or reflective in such devices.

As used herein, "top" means the farthest from the substrate, whereas "bottom" means the closest to the substrate. For example, with respect to a device having two electrodes, the bottom electrode is the electrode closest to the substrate and is typically the first electrode fabricated. The bottom electrode has two surfaces, closest to the bottom surface of the substrate and away from the top surface of the substrate. Where the first layer is described as being "configured over" the second layer, the first layer is configured to be remote from the substrate. There may be other layers between the first and second layers unless the first layer is designated to be "physically contacted" with the second layer. For example, a cathode can be described as being "configured over" an anode, even with various organic layers in between.

As used herein, "solution treatable" means capable of dissolving, dispersing or transporting in a liquid medium, and/or depositing therefrom, either in solution or as a suspension.

As used herein, and as is generally understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "highest occupied molecular orbital" (HOMO) or "minimum unoccupied molecule" The track "(LUMO) energy system" is greater than "or higher than" the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured in terms of the negative energy relative to the vacuum level, the higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Likewise, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On the conventional energy level diagram, the vacuum energy level is at the top, and the LUMO energy level of one material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy system shows closer to the top of such a graph than the "lower" HOMO or LUMO energy level.

Carbene ligands are well known in organometallic chemistry and are used to produce a wide range of thermally stable catalytic species. Carbonene ligands have been employed as reactive groups, directly involved in the catalytic reaction, and acted as a stabilizer for metals in specific oxidation states or coordination geometries. However, the use of carbene ligands is not well known in photochemistry.

One of the problems with many existing organic electroluminescent compounds is that they are not sufficiently stable for use in commercially available devices. This is especially true for phosphorescent emissive materials that emit in the blue portion of the spectrum. One item of the present invention is to provide an organic emissive compound having improved stability. One item of the present invention is to provide an organic emissive compound that emits light having various spectra, including high energy spectra, such as blue, in a stable manner.

The present invention is directed to an organic light-emitting device having an emissive layer comprising a phosphorescent organometallic emissive material having at least one tridentate ligand bonded to a metal center via at least one carbene-metal bond. In a preferred embodiment, the emissive material comprises two tridentate ligands bonded to a metal center, which may be the same or different, wherein at least one of the tridentate ligands has a carbene-metal bond.

In a preferred embodiment, the present invention is directed to an organic light-emitting device comprising an anode, a cathode, and a phosphorescent emitting region disposed between the anode and the cathode, wherein the emitting region comprises an emissive material having the formula I:

among them:

M is a second or third column transition metal;

L is an auxiliary ligand;

Ring A is selected from the group consisting of:

(a) an 8- to 12-membered bicyclic group having 3 to 5 ring heteroatoms;

(b) an 11- to 18-membered tricyclic group having 3 to 6 ring heteroatoms;

(c) a 11- to 14-membered fused tricyclic group;

(d) a 14- to 18-membered fused tetracyclic group;

Each R ^A is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C (O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; a is 0 to 4 Ring B is selected from the group consisting of a 5- or 6-membered cyclic group, an 8- to 12-membered bicyclic group, an 11- to 18-membered tricyclic group, and an 11- to 14-membered fused group. a tricyclic group and a 14- to 18-membered fused tetracyclic group; each R ^B group is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N (R' ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si (R") ₃ , halo, aryl and heteroaryl; b is 0 to 4; X ¹ is selected from CR ¹ and N; X ² is selected from CR ² and N; X ³ is selected from CR ³ and N; R ¹ , R ² and R ³ are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C (O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl Or R ¹ and R ² or R ² together with R ³ to form a 5- or 6-membered cyclic group, 8- to 10-membered fused bicyclic ring a group, 11- to 14-membered fused tricyclic group, which may optionally be substituted by one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O -R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR ', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; additionally or alternatively, R ¹ is taken together with R ^B to form a 5- or 6-membered cyclic group or 8 - to a 10-membered fused bicyclic group; additionally or alternatively, R ^{3 is} used together with R ^A to form a 5- or 6-membered cyclic group or a 8- to 10-membered fused bicyclic ring a radical; each R' is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; each R" is independently selected from H, alkyl, alkenyl, alkynyl and an aralkyl group; n is 1 or 2; and m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0.

Detailed description

In general, an OLED comprises at least one organic layer disposed between an anode and a cathode and electrically connected to them. When a current is applied, the anode injects holes, and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are positioned on the same molecule, an "exciter" is formed, which is a localized electron-hole pair having an excited state. When the excitons relax, the light is emitted via a light emission mechanism. In some cases, an exciton can be localized on an excimer or an excited complex molecule. Non-radioactive mechanisms, such as thermal relaxation, may also be present, but are generally considered to be undesirable.

The original OLEDs used an emitting molecule that emits light from its singlet state ("fluorescent"), as disclosed in, for example, U.S. Patent No. 4,769,292, the disclosure of which is incorporated herein in its entirety. Fluorescent emissions typically occur in a timeframe of less than 10 nanoseconds.

Recently, OLEDs having an emissive material that emits light from a triplet state ("phosphor") have been confirmed. Baldo et al., "Highly Effective Phosphorescence Emission from Organic Electroluminescent Devices," Nature, Vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Based on Electrophosphorescence" A highly efficient green organic light-emitting device, "Appl. Phys. Lett., Vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), which is incorporated by reference in its entirety. Phosphorescence can be referred to as a "taboo" transition because this transition needs to change in the state of rotation, and quantum mechanics shows that such a transition is disadvantageous. Thus, phosphorescence typically occurs in a time architecture that exceeds at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiation lifetime of phosphorescence is too long, the triplet state can be attenuated by a non-radioactive mechanism such that no light is emitted. Organic phosphorescence is also often found at very low temperatures in molecules containing heteroatoms with unshared electron pairs. 2,2'-bipyridyl is such a molecule. Non-radioactive decay mechanisms are typically temperature dependent such that organic materials that exhibit phosphorescence at liquid nitrogen temperatures typically do not exhibit phosphorescence at room temperature. However, as confirmed by Baldo, this problem can be solved by choosing a phosphorescent compound that does emit phosphorescence at room temperature. Representative emissive layers include doped or undoped phosphorescent organometallic materials, such as in U.S. Patent Nos. 6,303,238 and 6,310,360; U.S. Patent Application Publication Nos. 2002-0034656; 2002-0182441; 2003-0072964; Revealed in /074015.

In general, the excitons identified in the OLED will be produced in a ratio of about 3:1, meaning about 75% triplet and 25% singlet. See Adachi et al., "Close to 100% internal phosphorescent efficiency in organic light-emitting devices," J. Appl. Phys., 90, 5048 (2001), which is incorporated by reference in its entirety. In many cases, singlet excitons can easily transfer their energy to a triplet excited state via an "intersystem transition", whereas triplet excitons cannot easily transfer their energy to a singlet excited state. Therefore, it is possible to theoretically use a phosphorescent OLED system for 100% internal quantum efficiency. In a fluorescent device, the energy of the triplet excitons is typically lost to a non-radiative decay process that heats the device, resulting in much lower internal quantum efficiency. An OLED system utilizing a phosphorescent material that emits light from a triplet excited state is disclosed, for example, in U.S. Patent No. 6,303,238, the disclosure of which is incorporated herein by reference.

Phosphorescence can be preceded by a transition from a triplet excited state to an intermediate non-triplet state from which emission decay occurs. For example, organic molecules coordinated to lanthanides often emit phosphorescence from an excited state that is localized on the lanthanide metal. However, such materials do not directly emit phosphorescence from the triplet excited state, but instead emit from the excited state of the atomic center of the lanthanide metal ion. A bismuth dicarboxylate complex is a group that describes these species types.

Phosphorescence from triplet states can be enhanced to outweigh fluorescence, in a manner that is limited, preferably by organic molecules that bind closely to atoms with high atomic order. This phenomenon, known as the heavy atom effect, is produced by a mechanism called rotational orbital coupling. Such a phosphorescence transition can be found from an excited metal-to-ligand charge transfer (MLCT) state of an organometallic molecule such as ginseng (2-phenylpyridine) ruthenium (III).

The term "triplet energy" as used herein refers to the energy corresponding to the highest energy characteristic identifiable in the phosphorescence spectrum of a particular material. The highest energy characteristic is not necessarily the absorption peak having the greatest intensity in the phosphorescence spectrum, but may be, for example, a local maximum of the clear shoulder on the high energy side of such an absorption peak.

The term "organic metal" as used herein is generally understood by those skilled in the art and as in, for example, "Inorganic Chemistry" (2nd Edition) by Gary L. Miessler and Donald A. Tarr, Prentice Hall (1998). ) shown in ). Thus, the term organometallic refers to a compound having an organic group bonded to a metal via a carbon-metal bond. This species does not include a self-coordinating compound which is a metal complex having only a donor bond derived from a hetero atom, such as an amine, a halide, a pseudohalide (CN, etc.). In fact, organometallic compounds, in addition to one or more carbon-metal bonds to organic species, typically comprise one or more donor bonds derived from a hetero atom. The carbon-metal bond to an organic species refers to a direct bond between a metal and a carbon atom of an organic group (such as a phenyl group, an alkyl group, an alkenyl group, etc.), but does not refer to an "inorganic carbon" such as CN or CO. Carbon metal key.

FIG. 1 shows an organic light emitting device 100. These figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, and protection. Layer 155 and cathode 160. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence.

Substrate 110 can be any suitable substrate that provides the desired structural properties. The substrate 110 can be flexible or rigid. The substrate 110 can be transparent, translucent or opaque. Plastic and glass are examples of preferred rigid substrate materials. Plastic and metal foil are examples of preferred flexible substrates. Substrate 110 can be a semiconductor material to aid in the fabrication of circuitry. For example, the substrate 110 can be a germanium wafer on which circuitry is fabricated to control the OLEDs that are subsequently deposited on the substrate. Other substrates can be used. The material and thickness of the substrate 110 can be selected to achieve the desired structural and optical properties.

The anode 115 can be any suitable anode that is sufficiently conductive to transport holes to the organic layer. The material of the anode 115 preferably has a work function greater than about 4 eV ("high work function material"). Preferred anode materials include conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. The anode 115 (and the substrate 110) can be sufficiently transparent to create a bottom emitting device. Preferably, the transparent substrate and anode combination is a commercially available ITO (anode) deposited on glass or plastic (substrate). The flexible and transparent substrate-anode combination is disclosed in U.S. Patent Nos. 5,844,363 and 6,602,540 B2, the entireties of each of which are incorporated by reference. The anode 115 can be opaque and/or reflective. Reflective anode 115 may be preferred for some top emitting devices to increase the amount of light emitted from the top of the device. The material and thickness of the anode 115 can be selected to achieve the desired conductivity and optical properties. Where the anode 115 is transparent, it may have a range of thicknesses for a particular material that is thick enough to provide the desired conductivity and that is sufficiently thin to provide the desired degree of transparency. Other anode materials and structures can be used.

The hole transport layer 125 may comprise a material capable of transporting holes. The hole transport layer 130 can be inherent (undoped) or doped. Doping can be used to enhance conductivity. The α-NPD and TPD systems are examples of intrinsic hole transport layers. An example of a p-doped hole transport layer is m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, as disclosed in US Patent Application Publication No. 2002 to Forrest et al. -0071963 A1, which is incorporated by reference in its entirety. Other hole transport layers can be used.

Emissive layer 135 can include an organic material that is capable of emitting light when current is passed between anode 115 and cathode 160. The emissive layer 135 preferably contains a phosphorescent emissive material, but a fluorescent emissive material can also be used. Phosphorescent materials are preferred because of the higher luminous efficiency associated with such materials. The emissive layer 135 may also comprise a host material that is capable of transporting electrons and/or holes, doped with an emissive material that traps electrons, holes, and/or excitons such that the exciton emits itself via a light emission mechanism. The material is slack. Emissive layer 135 can comprise a single material that combines transport and emission properties. Emission layer 135 may comprise other materials, such as dopants that modulate the emission of the emissive material, whether the emissive material is a dopant or a primary component. Emissive layer 135 can comprise a plurality of emissive materials capable of emitting a desired spectrum in combination. Examples of the phosphorescent emissive material include Ir(ppy) ₃ . Examples of fluorescent emissive materials include DCM and DMQA. Examples of the host material include Alq ₃ , CBP, and mCP. Examples of emissive and host materials are disclosed in U.S. Patent No. 6, 303, 238 to the disclosure of U.S. Pat. The emissive material can be added to the emissive layer 135 in a variety of ways. For example, a small emitting molecule can be incorporated into a polymer. This can be achieved in several ways: by doping small molecules into individual or different molecular species into the polymer; or by incorporating small molecules into the backbone of the polymer to form a copolymer; or via Small molecules bind to the polymer as pendant groups. Other emissive layer materials and structures can be used. For example, a small molecule emissive material can exist as the core of a dendrimer.

Many of the emissive materials that can be used contain one or more ligands bonded to the metal center. A ligand may be referred to as "photoactive" if it directly contributes to the photoactive nature of the organometallic emissive material. A "photoactive" ligand can be used in conjunction with a metal to provide an energy level from which the electrons move when a photon is emitted. Other ligands may be referred to as "auxiliary." Auxiliary ligands can alter the photoactive nature of the molecule, for example by shifting the energy level of the photoactive ligand, but the ancillary ligand does not directly provide an energy level involved in light emission. A photoactive ligand in one molecule may be auxiliary in the other. These definitions of photoactivity and assist are intended as non-limiting theories.

Electron transport layer 145 can comprise a material that is capable of transporting electrons. Electron transport layer 145 can be inherent (undoped) or doped. Doping can be used to enhance conductivity. Alq ₃ is an example of an intrinsic electron transport layer. An example of an n-doped electron transporting layer is a Li-doped BPhen at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2002-0071963 A1, to the name of They are incorporated by reference in their entirety. Other electron transport layers can be used.

The charged component of the electron transport layer can be selected such that electrons can be efficiently injected from the cathode into the LUMO (lowest unoccupied molecular orbital) energy level of the electron transport layer. The "charged component" is a material responsible for the LUMO energy level that actually transports electrons. This component can be a base material or it can be a dopant. In general, the LUMO energy level of the organic material can be characterized by the electron affinity of the material, and in general, the relative electron injection efficiency of the cathode can be characterized by the work function of the cathode material. This means that the preferred properties of the electron transport layer and the adjacent cathode can be specified from the viewpoint of the electron affinity of the charged component of the ETL and the work function of the cathode material. In particular, in order to achieve high electron injection efficiency, the work function of the cathode material is preferably no more than about 0.75 eV, more preferably no more than about 0.5 eV, of the charge component of the electron transport layer. Similar considerations apply to any layer in which electrons are being injected.

Cathode 160 can be any suitable material or combination of materials known in the art such that cathode 160 is capable of conducting electrons and injecting them into the organic layer of device 100. Cathode 160 can be transparent or opaque and can be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 can be a single layer or can have a composite structure. 1 shows a composite cathode 160 having a thin metal layer 162 and a thicker conductive metal oxide layer 164. Among the composite cathodes, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known in the art. U.S. Patent Nos. 5,703,436, 5, 707, 745, 6, 548, 956 B2 and 6, 576, 134 B2, incorporated herein by reference inco Transparent conductive sputter deposited ITO layer. The portion of the cathode 160 that is in contact with the underlying organic layer, whether or not it is a single layer cathode 160, the thin metal layer 162 of the composite cathode or some other component, is preferably a material having a work function of less than about 4 eV ("low work function" Made of material"). Other cathode materials and structures can be used.

A blocking layer can be used to reduce the number of charge carriers (electrons or holes) and/or excitons exiting the emissive layer. The electron blocking layer 130 may be disposed between the emission layer 135 and the hole transport layer 125 to block electrons from leaving the emission layer 135 in the direction of the hole transport layer 125. Likewise, the hole blocking layer 140 may be disposed between the emissive layer 135 and the electron transport layer 145 to block holes from exiting the emissive layer 135 in the direction of the electron transport layer 145. The blocking layer can also be used to block the diffusion of the excitons away from the emissive layer. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147, issued to U.S. Pat.

As used herein, and as understood by those skilled in the art, the term "blocking layer" means that the layer provides a barrier that significantly inhibits the transport of charge carriers and/or excitons through the device, rather than It is pointed out that this layer must completely block charge carriers and/or excitons. The presence of such a barrier layer in the device can result in substantially higher efficiency when compared to similar devices lacking a barrier layer. The blocking layer can also be used to limit emission to the desired OLED region.

In general, the implant layer comprises a material that improves the injection of charge carriers from a layer, such as an electrode or an organic layer, into an adjacent organic layer. The injection layer can also perform a charge transport function. In device 100, hole injection layer 120 can be any layer that will improve the injection of holes from anode 115 into hole transport layer 125. CuPc is an example of a material that can be used as a hole injection layer, from the ITO anode 115 and other anodes. In device 100, electron injection layer 150 can be any layer of the injected electron transport layer 145 that will improve electrons. LiF/Al is an example of a material that can be used as an electron injecting layer, from an adjacent layer to an electron transporting layer. Other materials or combinations of materials can be used for the injection layer. Depending on the type of device, the injection layer can be configured at a different location than that shown in device 100. Further examples of the injection layer are provided in U.S. Patent Application Ser. The hole injection layer may comprise a solution deposited material, such as a spin-on polymer, such as PEDOT:PSS, or it may be a vapor deposited small molecule material such as CuPc or MTDATA.

A hole injection layer (HIL) can planarize or wet the anode surface to provide effective hole injection from the anode into the hole injection material. The hole injection layer may also have a charge-bearing component having a HOMO (highest occupied molecular orbital) energy level, as defined by its relative ionization potential (IP) energy as described herein, advantageously with one of the HILs. Adjacent anode layers on the sides, and hole transport layers on opposite sides of the HIL match. The "charged component" is the material responsible for the HOMO energy level that actually transports holes. This component can be a base material for the HIL, or it can be a dopant. The use of a doped HIL system allows the dopant to be selected for its electrical properties, and the host system is selected for morphological properties such as wetting, flexibility, toughness, and the like. A preferred property with respect to the HIL material is that voids can be effectively injected into the HIL material from the anode. In particular, the charged component of the HIL preferably has an IP greater than the IP of the anode material of no more than about 0.7 eV. More preferably, the charge component has an IP greater than the anode material of no more than about 0.5 eV. Similar considerations apply to any layer in which holes are being injected. The HIL material is further distinguished from conventional hole transport materials, which are typically used in the hole transport layer of OLEDs because such HIL materials can have hole conductance substantially lower than that of conventional hole transport materials. Sex. The thickness of the HIL of the present invention can be thick enough to help planarize or wet the surface of the anode layer. For example, a HIL thickness as low as 10 nanometers is acceptable for very smooth anode surfaces. However, since the anode surface tends to be extremely rough, a HIL thickness of up to 50 nm may be desirable in some cases.

The protective layer can be used to protect the underlying layers during subsequent processing. For example, the method used to make the metal or metal oxide top electrode can damage the organic layer, and the protective layer can be used to reduce or eliminate such damage. In device 100, protective layer 155 can reduce damage to the underlying organic layer during fabrication of cathode 160. The protective layer preferably has a high carrier mobility with respect to the type of carrier (electrons in device 100) it transports such that it does not significantly increase the operating voltage of device 100. CuPc, BCP and various metal phthalocyanines are examples of materials that can be used in the protective layer. Other materials or combinations of materials can be used. The thickness of the protective layer 155 is preferably sufficiently thick that there is little or no damage to the underlying layer due to the process occurring after the organic protective layer 160 is deposited, but not so thick as to significantly increase the operation of the device 100. Voltage. The protective layer 155 can be doped to increase its conductivity. For example, the CuPc or BCP protective layer 160 may be doped with Li. A more detailed description of the protective layer can be found in U.S. Patent Application Serial No. 09/931,948, the entire entire disclosure of which is incorporated herein by reference.

Figure 2 shows the inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED type has a cathode disposed above the anode and the device 200 has a cathode 215 disposed below the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described for device 100 can be used in corresponding layers of device 200. FIG. 2 is an example of how some layers may be omitted from the structure of device 100.

The simple laminated structure illustrated in Figures 1 and 2 is provided by way of non-limiting example, and it is to be understood that the specific embodiments of the present invention can be used with a wide variety of other structures. The particular materials and structures described are exemplary in nature and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or some layers may be omitted altogether, based on design, performance, and cost factors. Other layers that are not explicitly described may also be added. Materials other than those specifically described may be used. While many of the examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials can be used, such as a mixture of host and dopant, or more generally a mixture. The layers can also have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, which may be described as a hole transport layer or a hole injection layer. In a specific embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise multiple layers of different organic materials as described, for example with respect to Figures 1 and 2.

Structures and materials that are not explicitly described may also be used, such as OLEDs composed of a polymeric material (PLED), as disclosed in U.S. Patent No. 5,247,190, issued to s. As a further example, an OLED having a single organic layer can be used. The OLEDs can be stacked, for example, as described in U.S. Patent No. 5,707,745, the entire disclosure of which is incorporated herein by reference. The OLED structure can deviate from the simple laminate structure shown in Figures 1 and 2. For example, the substrate can include an angled reflective surface to improve the outer structure, such as the platform structure described in U.S. Patent No. 6,091,195, the entire disclosure of which is incorporated herein by reference. The pit structure is incorporated by reference in its entirety.

Any of the various embodiments may be deposited by any suitable method unless otherwise indicated. For organic layers, the preferred methods include thermal evaporation, ink jetting, as described in U.S. Patent Nos. 6,013,982 and 6,087,196, the entireties of each of each of each of And U.S. Patent No. 6,337,102, the disclosure of which is incorporated herein by reference in its entirety in the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire The full text is incorporated by reference. Other suitable deposition methods include spin coating and other solution based methods. The solution based process is preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. The preferred patterning method includes the deposition of a cap, and the like, as described in U.S. Patent Nos. 6,294,398 and 6,468,819, the entireties of each of which are incorporated by reference in their entirety in the entire entire entire entire entire entire entire entire entire disclosure . Other methods can also be used. The materials to be deposited may be modified so that they are compatible with the particular deposition process. For example, substituents, such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, can be used in small molecules to enhance their ability to be solution treated. A substituent having 20 carbons or more may be used, and 3 to 20 carbons are preferred. Materials having an asymmetrical structure may have better solution processability than those having a symmetrical structure because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.

The molecules disclosed herein may be substituted in a number of different ways without departing from the scope of the invention. For example, a substituent may be added to a compound having two or more mono-, di-, and/or tridentate ligands such that after the addition of the substituent, a mono-, bi-, and/or tridentate ligand One or more of the lines are joined together to form, for example, a tetra- or hexa-ligand. Other such links can be formed. This type of linkage may increase stability relative to similar compounds that do not have linkages, as is generally recognized by the art as "chelating".

Devices made in accordance with embodiments of the present invention can be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, light for internal or external illumination and/or signaling, on-head displays, Fully transparent display, flexible display, laser printer, telephone, mobile phone, personal digital assistant (PDA), laptop, digital camera, camera-recorder combination, viewfinder, microdisplay, Vehicles, large wall, cinema or stadium screen or sign. Various control mechanisms can be used to control the devices made in accordance with the present invention, including passive substrates and active substrates. Many devices are intended for use in a temperature range that is comfortable for humans, such as 18 ° C to 30 ° C, and more preferably at room temperature (20-25 ° C).

The materials and structures described herein can have applications on devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photodetectors, may employ such materials and structures. More generally, organic materials, such as organic transistors, may be employed in this material and structure.

The present invention is directed to a device having an emissive layer comprising a phosphorescent organometallic emissive material having at least one tridentate ligand bonded to a metal center via at least one carbon-metal bond. The metal center is selected from the second and third columns of transition metals, and is preferably selected from the group consisting of Ru, Os, Re, Rh, Ir, Pd, and Pt. In a particular embodiment, M is selected from the group consisting of Os and Ru, and in still more preferred embodiments, M is Os. The emissive material may additionally contain an auxiliary ligand to fill the coordination sphere of the metal center. In a preferred embodiment, the emissive material comprises two tridentate ligands bonded to a metal center, which may be the same or different, wherein at least one of the tridentate ligands has a carbon-metal bond. In a particularly preferred embodiment, the metal center is tantalum. This device may contain other emissive materials, which may be phosphorescent emissive materials or fluorescent emissive materials.

In a preferred embodiment of the invention, the carbon-metal bond to the tridentate ligand of the emissive material is a carbene-metal bond. Thus, in this particular embodiment, the emissive material comprises at least one tridentate ligand bonded to the metal center via at least one carbene-metal bond. The two other bonds to the metal center may be selected from (i) a coordinate bond derived from a hetero atom selected from N, O, S, and P, and (ii) a carbon-metal bond not being a carbene-metal bond, ( Iii) a carbene-metal bond, or any combination thereof.

The term "carbene" as used herein refers to a compound having a divalent carbon atom which, when not coordinated to a metal, has only six electrons in its valence electron layer. The available motion system for determining whether the ligand contains a carbene-metal bond is a mentally decomposed complex into a metal segment and a ligand. Then, it is determined whether the carbon atom in the ligand previously bound to the metal is a neutral divalent carbon atom in a destructed state. The resonant form of the preferred embodiment can be displayed as:

This carbene definition is not limited to metal-carbene complexes synthesized from carbenes, but is intended to focus on orbital structures and electron distributions associated with carbon atoms bonded to metals. This definition recognizes that "carbene" is technically not bivalent when incorporated into a metal, but is bivalent if it is detached from the metal. While many such compounds are obtained by first synthesizing a carbene and then combining it to a metal synthesis, this definition is intended to encompass compounds having similar orbital structures and electronic configurations synthesized by other methods. Lowry and Richardson, Mechanisms and Theory of Organic Chemistry 256 (Harper and Row, 1976) define "carbene" in a manner consistent with the manner in which this term is used herein. Some references may define "carbene" as a carbon ligand that forms a double bond to a metal. Although this definition is not used in this application, there may be some overlap between the two definitions. A variety of representations are used to characterize linkages in such carbenes, including where curved lines are used to indicate partial multiple bonds between carbene carbon and adjacent heteroatoms.

Carboolefin ligands are particularly desirable in OLED applications due to the high thermal stability exhibited by the metal-carbene complexes. The hexacarbene, which behaves almost like an electron-donating group, typically binds strongly to the metal, thus forming a composite that is more thermally stable than, for example, the previous cyclometallated composite used as a phosphorescent emitter.

Furthermore, due to the nature of the carbene-metal bond, the emission molecule comprising a carbene-metal bond can have increased stability, for example, in comparison to a compound that is a non-carbene analog. It is further believed that the emission spectrum of a molecule containing a carbene-metal bond may be different from that of an analog having no carbene.

The metal-carbene complex can be tailored to emit a plurality of spectra from the near-ultraviolet light across the entire visible spectrum by the choice of substituents and/or chemical groups on the ligand. More importantly, saturated blue emission with an absorption peak wavelength of about 450 nm is now available. Since salty recognition is substantially easier to reduce than increasing triplet energy by adjusting the emissive compound, the ability to fabricate a stable blue emitter at such high energies also allows red shifting of the emission by reducing energy. The possibility of getting any color.

The appropriate selection of substituents and/or chemical groups attached to the carbene ligand can also minimize quantum efficiency losses associated with increased temperature. The observable difference in the lifetime metric between room temperature and emission at low temperatures (e.g., 77K) is due to the non-radioactive quenching mechanism that competes with phosphorescence. It is further believed that this quenching mechanism is thermally activated, so that at a relatively cold temperature of about 77 K, the energy loss due to quenching is not a problem, and the quantum efficiency is about 100%. Suitable substituents on carbene ligands, or doping in relatively rigid matrices, as described in Turro, "Modern Molecular Photochemistry", University Science Books, Inc. (1991), 109-10 The quantum efficiency can be increased at room temperature and correspondingly shows a longer lifetime.

In some embodiments, the triplet energy of the carbene complex has a corresponding wavelength in the dark blue or ultraviolet (UV) portion of the spectrum. In some embodiments, the phosphorescent emissive compound has a triplet energy corresponding to a wavelength of less than 450 nanometers. In a preferred embodiment, the triplet energy system corresponds to a wavelength of less than 440 nanometers, and in still more preferred embodiments, it corresponds to a wavelength of less than 400 nanometers, which is believed to be in the UV region of the spectrum. Medium, because the salt letter 400 nm represents the cutoff between the UV and visible regions of the spectrum. This high triplet energy allows these compounds to be used to optically pump down the conversion layer. For such applications, the overlap is preferably between the emission spectrum of the ultraviolet carbene compound and the absorption spectrum of the down conversion layer. When about 50% of the overall spectral curve of the normalized electroluminescence of the device is at a wavelength of less than about 450 nm, there is sufficient energy to optically pump the down conversion layer. More than 90% of the emission is better produced below 440 nm, as disclosed herein. Preferably, 50% of the normalized electroluminescence spectral curve is less than about 440 nanometers, and more preferably less than about 400 nanometers. The wavelength cutoff frequency mentioned above is not intended to be an absolute limitation as it depends on the energy of the material to be pumped. It is believed that such emissions can also occur at room temperature.

Salty strong metal-carbon bonds also cause large rotational-orbital coupling in the metal carbene composite. Furthermore, the triplet energy of the coordinated carbenes was confirmed to be significantly higher than the pyridine analog. Even at room temperature, this emission can be in the near ultraviolet range of the spectrum. Here, the Xianxin metal carbene complex may be able to emit at the same high energy due to strong metal-ligand bonding with the carbene ligand.

The stability of the metal-carbene complex can also allow for increased susceptibility to the type of ligand and metal that can be used as a phosphorescent emitter in an OLED. Strong metal-carbene linkages can allow a variety of metals to form useful phosphorescent composites having carbene ligands to achieve novel emissive compounds.

The emissive material of the present invention comprises a tridentate ligand as a photoactive ligand. The ligand system is referred to as "photoactive" and is believed to contribute to the photoactive nature of the emissive material. The emissive material can further comprise an auxiliary ligand. These coordination groups are referred to as "auxiliaries" because they recognize the photoactive nature of the molecule and directly contribute to the photoactive properties. The definition of photoactivity and aid is intended as a non-limiting theory. The ancillary ligands can be selected from those disclosed in the following references:

U.S. Patent Application Publication No. 2002-0034656 (K&K 10020/15303), Figure 11-50, U.S. Patent Application Publication No. 2003-0072964 (Thompson et al.), paragraphs 7-132; and Figures 1-8; U.S. Patent Application Publication 2002-0182441 (Lamansky et al.), paragraphs 13-165, including Figures 1-9(g); U.S. Patent 6,420,057 B1 (Ueda et al.), column 1, line 57 to column 88, line 17, including compounds I-1 to XXIV-12; U.S. Patent 6,383,666 B1 (Kim et al.), col. 2, line 9 to column 21, line 67; U.S. Patent Application Publication No. 2001-0015432 A1 (Igarashi et al.), paragraph 2 57, comprising compounds (1-1) to (1-30); U.S. Patent Application Publication No. 2001-0019782 A1 (Igarashi et al.), paragraphs 13-126, including compounds (1-1) to (1-70) and (2-1) to (2-20); U.S. Patent Application Publication No. 2002-0024293 (Igarashi et al.), paragraphs 7-95, including the general formula KI to K-VI and the example compounds (K-1) to (K) -25); U.S. Patent Application Publication No. 2002-0048689 A1 (Igarashi et al.), paragraph 5-134, including Compound 1-81 and Example Compounds (1-1) to (1-81); U.S. Patent Application Publication No. 2002 -0063516 (Tsuboyama et al.), paragraphs 31-161, including each Compound 1-16; U.S. Patent Application Publication No. 2003-0068536 (Tsuboyama et al.), paragraphs 31-168, including each of the compounds of Tables 1-17, corresponding to EP-1-239-526-A2; U.S. Patent Application Bulletin 2003-0091862 (Tokito et al.), paragraph 10-190, including each of the compounds in Tables 1-17, corresponding to EP-1-239-526-A2; US Patent Application Publication No. 2003-0096138 (Lecloux et al.) , paragraphs 8-124, including Figures 1-5; U.S. Patent Application Publication No. 2002-0190250 (Grushin et al.), paragraph 9-191; U.S. Patent Application Publication No. 2002-0121638 (Grushin et al.), paragraph 8-125; U.S. Patent Application Publication No. 2003-0068526 (Kamatani et al.), paragraphs 33-572, including each of the compounds in Tables 1-23; U.S. Patent Application Publication No. 2003-0141809 (Furugori et al.), paragraphs 29-207; Application Gazette 2003-0162299 A1 (Hsieh et al.), paragraph 8-42; WO 03/084972 (Stossel et al.), Examples 1-33; WO 02/02714 A2 ((Petrov et al.), pp. 2-30 , including each of the compounds in Tables 1-5; EP 1-191-613 A1 (Takiguchi et al.), paragraphs 26-87, including each of the compounds in Tables 1-8 (equivalent to U.S. Patent Application Publication No. 2) 002-0064681); and EP 1-191-614 A2 (Tsuboyarna et al.), paragraphs 25-86, including each of the compounds in Tables 1-7; which are incorporated herein by reference in its entirety.

In a preferred embodiment, the present invention is directed to an organic light-emitting device comprising an anode, a cathode, and a phosphorescent emitting region disposed between the anode and the cathode, wherein the emitting region comprises an emissive material having the formula I:

among them:

M is a second or third column transition metal;

L is an auxiliary ligand;

Ring A is selected from the group consisting of:

(a) an 8- to 12-membered bicyclic group having 3 to 5 ring heteroatoms;

(b) an 11- to 18-membered tricyclic group having 3 to 6 ring heteroatoms;

(c) a 11- to 14-membered fused tricyclic group;

(d) a 14- to 18-membered fused tetracyclic group;

Each R ^A is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C (O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R, Si(R") ₃ , halo, aryl and heteroaryl; a is 0 to 4; Ring B is selected from the group consisting of a 5- or 6-membered cyclic group, an 8- to 12-membered bicyclic group, an 11- to 18-membered tricyclic group, and an 11- to 14-membered fused three. a cyclic group and a 14- to 18-membered fused tetracyclic group; each R ^B group is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si ( R") ₃ , halo, aryl and heteroaryl; b is 0 to 4; X ¹ is selected from CR ¹ and N; X ² is selected from CR ² and N; X ³ is selected from CR ³ and N ; R ¹ , R ² and R ³ are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C ( O) OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl ; alternatively, R ¹ and R ² or R ² and R ³ taken together form a 5- or 6-membered cyclic group, a 8- to 10-membered fused bicyclic via a group, 11- to 14-membered fused tricyclic group, which may optionally be substituted by one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O- R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR' , SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; additionally or alternatively, R ¹ is taken together with R ^B to form a 5- or 6-membered cyclic group or 8- To a 10-membered fused bicyclic group; additionally or alternatively, R ³ is taken together with R ^A to form a 5- or 6-membered cyclic group or 8- to 10-membered fused bicyclic ring a group; each R' is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; each R" is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aralkyl group; n is 1 or 2, and m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0.

All numerical ranges, such as those given for n and m, are inclusively encompassing the entire range. Thus, for example, the range between 0-4 includes the values 0, 1, 2, 3, and 4.

In a preferred embodiment of the invention, the M system is selected from the group consisting of Ru, Os, Re, Rh, Ir, Pd, and Pt. In a particular embodiment, M is selected from the group consisting of Os and Ru, and in still more preferred embodiments, M is Os. With respect to certain preferred embodiments, Os is a preferred metal because it is relatively susceptible to oxidation. In a further preferred embodiment, the emissive material has a positive ratio of about -0.7 volts, more preferably about -0.3 volts, and more preferably an oxidation potential of about 0 volts, relative to dicyclopentanol. Diene iron / dipenta iron ion cation.

In another preferred embodiment, the compound according to formula I is a neutral compound. Neutral compounds can have the advantage of being easier to handle in the manufacture of the device as it can be deposited using sublimation techniques.

Where the compound according to formula I is a charged compound, the compound will contain a counterion to balance the charge. In this case, the metal complex will have a positive charge ranging from 1 ⁺ to 6 ⁺ , and preferably from 1 ⁺ to 3 ⁺ . The counterion can be selected from any suitable anion that does not interfere with the function of the compound in the device, for example as an emissive material. The anion is selected to be electrochemically inert and covers the operating voltage range of the device. Preferred counter anions are typically weakly coordinating anions. The term "weakly complex anion" is per se known in the art and generally refers to a large, large anion capable of delocalizing the negative charge of an anion. Suitable weakly coordinating anions, not all of which are considered to be large, include but are not limited to: PF ₆ ^- , BF ₄ ^- , SbCl ₆ ^- , trifluoromethanesulfonate, BAr ₄ ^- (Ar = C ₆ F ₅ ) , BAr' ₄ ^- (Ar' = 3,5-bis(trifluoromethyl)phenyl, etc. The weak coordination property of such an anion is known to those skilled in the art and is described in the literature (S Strauss et al., Chem. Rev., 1993, 93, 927).

In a particular embodiment of the invention, wherein n is 1, m is a selected integer to satisfy the valence bond of M; a plurality of L may be the same or different; and the (L) _m system generally comprises 6-electron for A single negative ligand or a ligand group.

In some embodiments of the invention, ring A is different from ring B. In a preferred embodiment of the invention, Ring A and Ring B are selected to be identical.

In a further embodiment of the invention, the emissive material has the formula I _a :

among them:

M is a second or third column transition metal;

L is an auxiliary ligand;

Ring A is selected from the group consisting of:

(a) an 8- to 12-membered bicyclic group having 3 to 5 ring heteroatoms;

(b) an 11- to 18-membered tricyclic group having 3 to 6 ring heteroatoms;

(c) a 11- to 14-membered fused tricyclic group;

(d) a 14- to 18-membered fused tetracyclic group;

Each R ^A is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C (O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; a is 0 to 4 ; Ring B is selected from the group consisting of:

(a) an 8- to 12-membered bicyclic group having 3 to 5 ring heteroatoms;

(b) an 11- to 18-membered tricyclic group having 3 to 6 ring heteroatoms;

(c) a 11- to 14-membered fused tricyclic group;

(d) a 14- to 18-membered fused tetracyclic group;

Each R ^B is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C (O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") 3 , halo, aryl and heteroaryl; b is 0 to 4 X ^l is selected from CR ¹ and N; X ² is selected from CR ² and N; X ³ is selected from CR ³ and N; and R ¹ , R ² and R ³ are independently selected from alkyl, alkenyl and alkyne. Base, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R′, SOR′, SO ₃ R′, Si(R”) ₃ , halo, aryl and heteroaryl; or R ¹ and R ² or R ² together with R ³ form a 5- Or a 6-membered cyclic group, a 8- to 10-membered fused bicyclic group, a 11- to 14-membered fused tricyclic group, which may optionally be substituted with one or more substituents The substituents are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C ( O) NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; additionally or alternatively, R ¹ and R ^B taken together to form a 5- or 6-membered cyclic group, or a 8- to 10-membered by Together bicyclic group; Additionally or alternatively, R ³ and R ^A are taken together to form a 5- or 6-membered cyclic group, or a 8- to 10-membered fused bicyclic group by group; each R ' Is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; each R" is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aralkyl: n is 1 or 2; and m is 0 to 3, wherein when n is 1, m is 1-3, and when n is 2, m is 0.

In a further preferred embodiment according to the compound of formula I, the metal center is bonded to two tridentate ligands (n=2, m=0) to obtain a compound of formula II:

Wherein X ¹ , X ² , X ³ , R ^A , R ^B , M, ring A , ring B, a and b are as described for the compound of formula I.

The compounds of the invention comprising two tridentate ligands are preferred. Such a compound is preferred because of its ligand configuration, which improves the stability of the material when incorporated into an organic light-emitting device. Moreover, such materials may have other advantages of being more stable in sublimation during preferred deposition techniques such as OVPD.

The term "5- or 6-membered cyclic group" refers to a five- or six-membered ring which may be saturated, partially unsaturated or aromatic, and optionally containing one or more ring heteroatoms.

When ring A (and ring B, in certain embodiments) is selected to be (a) an 8- to 12-membered bicyclic group having 3 to 5 ring heteroatoms, a bicyclic group The ring can be fused as appropriate. In a preferred embodiment, the ring of the bicyclic group is aromatic. Preferred bicyclic groups having 3 to 5 ring heteroatoms may be selected from the following ring systems:

Wherein R ^A2 is a 5- to 6-membered cyclic group; and subst represents a substituent selected from the group consisting of halo, alkyl, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amino group. , NO ₂ and OR.

The term "8- to 10-membered fused bicyclic group" refers to an eight to ten membered ring system in which each ring system is fused (ie, the ring shares two adjacent ring atoms) and It is saturated, partially unsaturated or aromatic, and optionally contains one or more ring heteroatoms.

When ring A (and ring B, in certain embodiments) is selected to be (b) an 11- to 18-membered tricyclic group having 3 to 6 ring heteroatoms, a tricyclic group The two rings can be fused as appropriate. In a preferred embodiment, the ring of the tricyclic group is aromatic. Preferred tricyclic groups having 3 to 5 ring heteroatoms may be selected from the following ring systems:

Wherein R ^A2 is a 5- to 6-membered cyclic group; and R _A3 is selected from the group consisting of 8- to 12-membered bicyclic groups.

The term "11- to 14-membered fused tricyclic group" means an eleven to fourteen member ring system in which each ring may be saturated, partially unsaturated or aromatic, and may optionally contain one or Multiple ring heteroatoms.

In certain embodiments, Ring A (and Ring B, in certain embodiments) is selected to be a (c) 11- to 14-membered fused tricyclic group. Preferably, the 11- to 14-membered fused tricyclic group can be selected from the following ring systems:

The term "14- to 18-membered fused tetracyclic group" means a fourteen to eighteen member ring system in which each ring may be saturated, partially unsaturated or aromatic, and may optionally contain one or Multiple ring heteroatoms.

In certain embodiments, Ring A (and Ring B, in certain embodiments) is selected to be a (d) 14- to 18-membered fused tetracyclic group. Preferably, the 14- to 18-membered fused tetracyclic group can be selected from the following ring systems:

In a further embodiment of the invention, the emissive material has the formula III:

Wherein: M is a second or third column transition metal; L is an auxiliary ligand; Y ¹ is selected from N and CR ⁴ ; Y ² is selected from N and CR ⁵ ; and R ⁴ and R ⁵ are independently selected from the group consisting of an alkane Base, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN , CF ₃ , NO ₂ , SO ₂ R′, SOR′, SO ₃ R′, Si(R”) ₃ , halo, aryl and heteroaryl; or R ⁴ and R ⁵ together form a 5- Or a 6-membered cyclic group, a 8- to 10-membered fused bicyclic group, a 11- to 14-membered fused tricyclic group, which may optionally be substituted with one or more substituents The substituents are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C ( O) NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ¹² is selected from alkane a group, an aryl group, an arylalkyl group, a cycloalkyl group, and a C(O)R'; the Z ¹ group is selected from N and CR ⁶ ; the Z ² system is selected from N and CR ⁷ ; and the R ⁶ and R ⁷ are independently selected from the group consisting of an alkane Base, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN , CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', S i(R") ₃ , halo, aryl and heteroaryl; or R ⁶ together with R ⁷ to form a 5- or 6-membered cyclic group, 8- to 10-membered fused bicyclic ring a group, 11- to 14-membered fused tricyclic group, which may optionally be substituted by one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O -R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR ', SO ₃ R', Si (R") ₃ , halo, aryl and heteroaryl; R ²² is selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and C(O)R'; X ¹ is selected from CR ¹ and N; X ² is selected from CR ² and N; X ³ is selected from CR ³ and N; and R ¹ , R ² and R ³ are independently selected from alkyl, alkenyl and alkynyl groups. , aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; or R ¹ and R ² or R ² together with R ³ form a 5- or a 6-membered cyclic group, a 8- to 10-membered fused bicyclic group, and a 11- to 14-membered fused tricyclic group, which may be optionally substituted with one or more substituents, Substitute Is selected from alkyl, alkenyl, alkynyl, aralkyl, OR ', N (R' ) 2, SR ', C (O) R', C (O) OR ', C (O) NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; additionally or alternatively, R ¹ and R ⁶ Used together to form a 5- or 6-membered cyclic group or an 8- to 10-membered fused bicyclic group; additionally or alternatively, R ^{3 is} used together with R ⁴ to form a 5- or 6-member a cyclic group or a 8- to 10-membered fused bicyclic group; each R' is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; R" is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aralkyl; n is 1 or 2; and m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n When it is 2, m is 0.

In certain preferred embodiments of the emissive material of Formula III, at least one of Y ₁ and Y ₂ is N. In a particular embodiment, the R ¹² system is further selected to be an aryl group.

In certain preferred embodiments of the emissive material of Formula III, at least one of Z ¹ and Z ² is N. In particularly preferred embodiments, R ²² is further selected based aryl group.

In other preferred embodiments of the emissive material of Formula III, the Y ¹ and Y ² lines are individually CR ⁴ and CR ⁵ , and R ⁴ and R ⁵ are employed together to form a 8- to 10 _- membered fused bicyclic ring. a group or a 11- to 14-membered fused tricyclic group optionally substituted with one or more substituents independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O- R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR' , SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl.

In other preferred embodiments of the emissive material of Formula III, the Z ¹ and Z ² systems are individually CR ⁶ and CR ⁷ , and R ⁶ and R ⁷ are employed together to form a 8- to 10-membered fused bicyclic ring. a group or a 11- to 14-membered fused tricyclic group optionally substituted with one or more substituents independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O- R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR' , SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl.

In a further embodiment of the invention, the emissive material has the formula IV:

Wherein: M is a second or third column transition metal; a broken line indicates an optional double bond; X ² is selected from CR ² or N; and R ² is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ⁵ is selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ⁷ is selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF3, NO ₂ , SO ₂ R', SOR', SO ₃ R', Si (R ") ₃ , halo, aryl and heteroaryl; R ¹² is selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and C(O)R'; R ¹³ and R ¹⁴ are independently selected from H , alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; additionally or alternatively, R ¹³ and R ¹⁴ form a fused 5- or 6-membered cyclic group, wherein the fused cyclic group is optionally substituted by one or more substituents selected from alkyl, alkenyl, alkyne Base, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R′, SOR′, SO ₃ R′, Si(R”) ₃ , halo, aryl and heteroaryl; R ²² is selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and C(O)R'; R ²³ and R ²⁴ are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O) R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aromatic And a heteroaryl group; additionally or alternatively, R ²³ and R ²⁴ form a fused 5- or 6-membered cyclic group, wherein the fused cyclic group is optionally substituted with one or more substituents, The substituent is selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O) NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; each R' is independently selected from H , alkyl, alkenyl, alkynyl, aralkyl And aryl and heteroaryl; and each R" is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aralkyl.

In a preferred embodiment of the invention, each of X ¹ , X ² and X3 is individually selected to be CR ¹ , CR ² , CR ³ .

Preferred substituents for aryl and heteroaryl include CF ₃ , CN, CH ₃ , F and phenyl. In a preferred embodiment, the substituent R ² is selected from the group consisting of CF ₃ , CN, CH ₃ , F, and phenyl, with CF ₃ and CN being particularly preferred.

In a preferred embodiment of the invention, the device comprises an emissive material selected from Group 1, Group 2 or Table I, which provides a density function theory (DFT) using a G98/B31yp/cep-31g basis combination. Calculations to obtain estimates of HOMO, LUMO, HOMO-LUMO gaps, singlet energy S1, and triplet energy T1 for various compounds of the invention.

A preferred embodiment includes a ruthenium complex containing two tridentate ligands, each having a bond to a metal center from a carbene and from an anionic benzene ring.

The term "halo" or "halogen" as used herein includes fluoro, chloro, bromo and iodo.

The term "alkyl" as used herein is intended to encompass both straight and branched chain alkyl groups. Preferred alkyl groups are those having from one to fifteen carbon atoms and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like. Further, the alkyl group may be optionally substituted by one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR, wherein Each R is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.

The term "cycloalkyl" as used herein is intended to encompass a cyclic alkyl group. Preferred cycloalkyl groups are those having 3 to 7 carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl and the like. Further, the cycloalkyl group may be optionally substituted with one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR.

The term "alkenyl" as used herein is intended to encompass both straight-chain and branched alkene groups. Preferred alkenyl groups are those having from two to fifteen carbon atoms. Further, the alkenyl group may be optionally substituted with one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR.

The term "alkynyl" as used herein is intended to encompass both straight-chain and branched alkyne groups. Preferred alkynyl groups are those having from two to fifteen carbon atoms. Furthermore, the alkynyl group may be optionally substituted by one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR.

The term "aralkyl" as used herein is intended to encompass alkyl groups having an aromatic group as a substituent. Further, the aralkyl group may be optionally substituted on the aryl group with one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine group, NO _{2 .} And OR.

The term "heterocyclic group" as used herein is intended to encompass a non-aromatic cyclic group. Preferred heterocyclic groups are those having 3 or 7 ring atoms, which contain at least one hetero atom, and include cyclic amines such as morpholinol, hexahydropyridyl, tetrahydropyrrolyl, etc., and rings. Ethers such as tetrahydrofuran, tetrahydropyran, and the like. Furthermore, a heterocyclic group may be optionally substituted by one or more substituents selected from halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine, NO ₂ and OR. .

The terms "aryl" or "aromatic group" as used herein are intended to encompass both monocyclic and polycyclic ring systems. A multi-ring ring may have two or more rings, wherein two carbons are shared by two adjacent rings (these rings are "fused"), at least one of which is aromatic, for example other rings may be rings Alkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl. Further, the aryl group may be optionally substituted with one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR.

The term "heteroaryl" as used herein is intended to encompass monocyclic heteroaromatic groups which may contain from one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, Oxazole, thiazole, triazole, pyrazole, pyridine, pyridyl And pyrimidine and the like. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are shared by two adjacent rings (these rings are "fused"), at least one of which is A heteroaryl group, for example, other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl, and includes, for example, quinoline, isoquinoline, indole, oxazole, and the like. Further, the heteroaryl group may be optionally substituted by one or more substituents selected from the group consisting of halo, CN, CO ₂ R, C(O)R, NR ₂ , cyclic-amine groups, NO ₂ and OR.

It should be understood that the various embodiments described herein are by way of example only, and are not intended to For example, many of the materials and structures described herein may be substituted by other materials and structures without departing from the spirit of the invention. It should be understood that the various theories as to why the invention works are not intended to be limiting. For example, the theory of charge transfer is not intended to be a limitation.

Substance definition:

As used herein, the abbreviation refers to a substance such as CBP: 4,4'-N,N-dicarbazole-biphenyl m-MTDATA 4,4',4"-para (3-methylbenzene) Benzoamino)triphenylamine Alq ₃ : 8-hhenyl-quinolinol aluminum Bphen: 4,7-diphenyl-1,10-diazepine n-BPhen: n-doped BPhen (doped with lithium) Hetero) F ₄ -TCNQ: tetrafluoro-tetracyano-quinodimethane p-MTDATA: p-doped m-MTDATA (doped with F ₄ -TCNQ) Ir(ppy) ₃ : ginseng (2- Phenylpyridine)-铱Ir(ppz) ₃ : 参(1-phenylpyrazolo, N,C(2')铱(III)BCP: 2,9-dimethyl-4,7-diphenyl -1,10-diazepine TAZ: 3-phenyl-4-(1'-naphthyl)-5-phenyl-1,2,4-triazole CuPc: copper phthalocyanine ITO: indium oxide Tin NPD: N,N'-diphenyl-N-N'-bis(1-naphthyl)-benzidine TPD: N,N'-diphenyl-N-N'-bis(3-tolyl) -benzidine BAIq: bis(2-methyl-8-hydroxyquinolyl) 4-phenylphenol aluminum (III) mCP: 1,3-N,N-dicarbazole-benzene DCM: 4-(dicyandi Ethylene)-6-(4-dimethylaminostyryl-2-yl)-4H-pyran DMQA: N,N'-dimethylquinacridone PEDOT:PSS: poly(3,4 - aqueous dispersion of poly(diethylenedioxythiophene) and polystyrene sulfonate (PSS) DTB 3,3'-di(benzene And phenanthrene-2-yl)biphenyl HIL4 fac-gin[2-(3-methyl-2-pyridyl-κN)phenyl-κC]铱(III)

experiment:

Specific representative embodiments of the invention will now be described, including how such embodiments may be practiced. It should be understood that specific methods, materials, conditions, process parameters, devices, etc., do not necessarily limit the scope of the invention.

Synthesis of ruthenium carbene complex 1 (Os1) Step 1: Os 1-A

In a three-neck 1000 ml round bottom flask, 19.1 g of benzimidazole, 25.0 g of 1,3-diiodobenzene, 1.46 g of copper (I) iodide, 44.7 g of potassium carbonate, and 2.77 g of 1,10-diazepine were added. And 500 ml of anhydrous N,N-dimethylformamide. The reaction mixture was heated to reflux under nitrogen over 2 days. After cooling to room temperature, the reaction was filtered and the solvent was removed from the filtrate by rotary evaporation. The crude product was purified by column chromatography eluting with 95% dichloromethane/methanol as solvent. The dissolved fractions containing the desired material are combined and the solvent is removed by rotary evaporation. The product was crystallized from a dichloromethane/ethyl acetate mixture. The product was collected by vacuum filtration (18 g) as a white solid.

Step 2 : Os 1-B

In a 1000 ml round bottom flask, 15 g of Compound A, 30 g of methyl iodide and 400 ml of N,N-dimethylformamide were added. The mixture was heated to about 60 ° C for 18 hours. The mixture was filtered and the solid was washed with ethyl acetate. The solid was then slurried in 400 mL of refluxing methanol, cooled and filtered to give 20 g of desired material as a white solid.

Step 3 : OsH ₄ (PPh ₃ ) ₃

In a 1000 ml 3-neck round bottom flask, 3.6 g of triphenylphosphine and 100 ml of ethanol were added. The mixture was heated to reflux and 1.0 g of ammonium hexachloroantimonate was added. A solution of 0.43 g of sodium borohydride in 50 ml of ethanol was then added dropwise. The reaction was refluxed for 30 minutes and then cooled to room temperature. The off-white solid was collected by vacuum filtration. The solid was washed successively with ethanol, water, ethanol and hexane.

Step 4 : Os 1

In a 250 ml 3-neck round bottom flask, 4.0 g of Compound B, 3.3 g of OsH ₄ (PPh ₃ ) 3 and 125 ml of N,N-dimethylformamide were added. The mixture was heated to reflux under nitrogen for 20 hours. The solvent was removed by rotary evaporation and the crude material was purified using EtOAc EtOAc EtOAc EtOAc. The fractions containing the desired product are combined and the solvent is removed by rotary evaporation. The product was crystallized from a mixture of ethyl acetate / hexane. The product was confirmed by mass spectrometry and ¹ H NMR.

The emission spectrum of Os1 which is a solution in toluene (degassed) at room temperature is shown in Fig. 3.

Example 2

osmium Synthesis of carbene complex OS2 step 1

To a solution of CuBr ₂ (26.8 g, 120 mmol) in anhydrous acetonitrile (500 mL), tris-butyl nitrite (21.1 mL, 160 mmol) was added dropwise at 0 ° C. 3-Amino-5-bromotrifluoride toluene (25 g, 104.1 mmol) was added dropwise. The mixture was stirred at 0 ° C for 1.5 hours and then at room temperature for 16 hours. The mixture was then concentrated in vacuo to one-half of its original volume and then poured into 1N HCl (EtOAc). This mixture was extracted with ether (400 mL). The organic layer was washed with 1N HCl, dried (Na ₂ SO _4), filtered, and concentrated in vacuo. The residue was purified by flash chromatography on silica formula column using hexane as the eluent, to obtain 18.33 g and OS2-A (57.8%).

Step 2

In a 1000 ml round bottom flask, 13.33 g of compound OS2-A , 12.43 g of benzimidazole, 1.668 g of copper (I) iodide, 3.15 g of 1,10-diazaphenanthrene, 59.93 g of cesium carbonate and 500 ml of N were added. N-dimethylformamide. The reaction mixture was heated to 150 ° C under nitrogen for 60 hours. After cooling to room temperature; the reaction was filtered and the solvent was removed from the filtrate by rotary evaporation. The crude product was purified by column chromatography eluting with EtOAc/EtOAc. The product OS2-B (10 g, 60%) was obtained as a white solid.

Step 3

In a 1000 ml round bottom flask, 8 g of compound OS2-B , 60 g of methyl iodide and 500 ml of N,N-dimethylformamide were added. The mixture was heated to 41 ° C for 70 hours. 200 ml of toluene was added to induce precipitation. The mixture was filtered, and the solid was washed with ether, to produce 9 g OS2-C (64%).

Step 4

In a 50 ml round bottom flask, 310 mg of the compound OS2-C , 230 mg of OsH ₄ (PPh ₃ ) ₃ and 35 ml of N,N-dimethylformamide were added. The mixture was heated to 150 ° C under nitrogen for 3 hours. The reaction mixture was poured into water (150 ml) and extracted with ether. The ether is removed by rotary evaporation. The residue was purified by column chromatography (SiO _2, 80% hexanes / ethyl acetate) to yield OS2.

The emission spectrum of Os2 as a solution in toluene (degassed) at room temperature is shown in Fig. 4.

Example 3 Synthesis of es-4

In a single neck 100 ml round bottom flask, 15 grams of 2,3 diaminonaphthalene and 30 milliliters of 99% formic acid were added. The mixture was heated to reflux for 3 hours. The mixture was extracted with ethyl acetate and water. The organic phase was discarded and the aqueous phase was neutralized with sodium hydroxide. The solid formed was filtered and washed with water and isopropyl alcohol. The desired product was purified by vacuum distillation to yield 12 g of naphthylcarbazole as a white solid.

In a three-neck 500 ml round bottom flask, 10 g of naphthylcarbazole, 8.9 g of 1,3-diiodobenzene, 0.56 g of copper iodide (I), 17.2 g of potassium carbonate, and 1.07 g of 1,10-two were added. Nitrofibrate and 200 ml of anhydrous N,N-dimethylformamide. The reaction mixture was heated to reflux under nitrogen for 18 h. After cooling to room temperature, the reaction was filtered. The solid was slurried in a mixture of water and isopropanol. The mixture was then filtered and washed with isopropanol to give 10 g of a white solid. The desired product was confirmed by ¹ H NMR.

The product was then dissolved in 500 ml of NMP. Approximately 30 grams of methyl iodide was added and the reaction was heated to about 80 °C over 36 hours. The mixture was allowed to cool and the solid was filtered then washed ethyl acetate.

In a 1-liter three-necked round bottom flask, 2.0 g of ammonium hexachloroantimonate, 8.4 g of triphenylphosphine, 120 ml of water and 300 ml of tri-butanol were added. The mixture was heated to reflux under nitrogen for 24 hours. After cooling to room temperature, the reaction mixture was filtered, and the solid was washed with water and then with ethanol. The green solid was allowed to air dry to give 4.8 g of OsCl ₂ (PPh ₃ ) ₃ .

In a 500 ml three-necked round bottom flask, 5 g of silver oxide, 5.0 g of es4i-3 and about 250 ml of anhydrous N,N-dimethylformamide were added. The mixture was heated to 60 ° C under nitrogen for 1.5 hours. After cooling to room temperature, 3.75 g of OsCl ₂ (PPh ₃ ) _{3 was} added to the flask. The mixture was heated to 100 ° C for 18 hours and then heated at 120 ° C for 6 hours. Dichloromethane was added and the solid was filtered. Water was added to the filtrate and the aqueous layer was extracted three times with dichloromethane. The combined organic fractions were dried with MgSO4, filtered and evaporated. This material was purified by column chromatography using 30% hexanes/dichloromethane as solvent. The desired fractions were combined and the solvent was removed to give s-4 , which was then crystallised from dichloromethane/hexane.

real Example 4 Preparation of es-7

step Step 1

In a three-necked flask, 3,5-dibromobenzonitrile (1 g, 3.86 mmol), N ¹ -phenylbenzene-1,2-diamine (1.42 g, 7.72 mmol), Pd ₂ (dba) ₃ (530 mg, 0.58 mmol), (2-biphenyl) di-tert-butylphosphine (345.5 mg, 1.158 mmol), sodium tris-butoxide (1 g) , 10.81 mmol) and anhydrous toluene (70 mL). The reaction mixture was stirred at room temperature under nitrogen for 24 h. The reaction mixture was cooled to 0.degree. C. by ice bath, and a solution of 1M HCl (10.81 ml) in ether was added to the mixture. The reaction mixture was filtered and the precipitate was collected and used in the next step without further purification.

Step 2

The product from Step 1 (1.8 g, 3.86 mmol), triethyl orthoformate (125 mL), cone. HCl (1 mL) and formic acid (s) were added to a 250 mL round bottom flask. The reaction was heated at 80 °C for 16 hours. The reaction mixture was concentrated in vacuo and EtOAc EtOAcjjjjjjj

Step 3

In a 100 ml round bottom flask, add ligand (1.12 g, 2 mmol), silver oxide (1.39 g, 6 mmol), (PPh ₃ ) ₃ OsCl ₂ (1.048 g, 1 mmol) And anhydrous DMF (50 ml). The reaction was heated to 150 ° C under nitrogen for 1.5 h. The reaction mixture was filtered, and the precipitate was washed ethyl acetate. The filtrate was concentrated, and to accept column chromatography (SiO _2, triethylamine pretreated in hexanes of 5% CH ₂ Cl ₂ in hexanes to of 50% CH ₂ Cl _2), to obtain es -7 (72 mg, 6%).

Example 5 Synthesis of es-8

In a 500 ml round bottom flask, 3,5-dibromobenzonitrile (10.0 g, 38.3 mmol), 4-nitrobenzimidazole (10.96 g, 92.0 mmol), copper iodide (I) (1.46 g, 7.7 mmol), 1,10 phenanthrene (1.39 g 7.7 mmol) with potassium carbonate (11.1 g, 80.4 mmol) and anhydrous dimethylformamide (100 mL). It was stirred at 125 ° C for 20 hours. The mixture was then allowed to cool to ambient temperature and filtered. The solid was washed with 19:1 dichloromethane-methanol (50 mL). The filtrate was concentrated in vacuo and the crude material was purified (jjjjjjjjjjjjjjjjjjjjjjj . ¹ H NMR (DMSO-d6) δ 9.10 (s, 2H), 9.09 (t, 1H), 8.64 (s, 2H), 8.47 (d, 2H), 8.25 (d, 2H), 7.44 (dd, 2H) ). MS(EI+)337.

In a 250 ml round bottom flask, 3,5-bis(3H-imidazo[4,5-b]pyridin-3-yl)benzonitrile (2.35 g, 6.97 mmol), anhydrous dimethyl group was added. Indoleamine (80 ml) and n-hexane iodide (15.3 ml, 104.6 mmol). It was stirred at 150 ° C for 20 hours and then concentrated in vacuo. Ethyl acetate (100 mL) was added and the solid was filtered and crystallised from methanol to give 3. <RTIgt; ¹ H NMR (DMF-d7) δ 11.0 (s, 2H), 9.50 (t, 1H), 9.03 (m, 3H), 8.92 (m, 2H), 4.93 (t, 4H), 2.20 (m, 4H) ), 1.56 (m, 4H), 0.88 (t, 6H). The ligand salt was converted to es-8 following a procedure similar to that used to prepare es-7 .

Example 6 Synthesis of es-9

step Step 1

In a three-necked flask, 3,5-dibromobenzonitrile (50 g, 0.19 mol), 1,2,4-triazole (26.5 g, 0.38 mol), copper iodide (3.62 g, 0.019 mol), trans-N,N'-dimethylcyclohexane-1,2-diamine (5.4 g, 0.038 mol), potassium phosphate (anhydrous, 161.3 g, 0.76 mol) and anhydrous DMF (600 ml). The reaction mixture was stirred under nitrogen and heated at 110 ° C for 24 hours, then cooled to room temperature. The solid was filtered and washed with DMF. The combined filtrate and washings were concentrated under vacuum. The residual solid was washed with ethyl acetate and purified by sublimation to give the desired product.

Step 2

The product from Step 1 (16.2 g, 0.068 mol), 1-iodohexane (144.2 g, 0.68 mol) and anhydrous DMF (350 mL) were then weighed from a 1 liter round bottom flask. The reaction mixture was heated in an oil bath at 150 ° C (bath temperature) for 18 hours. It was allowed to cool and concentrated under vacuum. The residual solid was recrystallized from methanol to give a ligand (27.6 g, 62%).

Step 3

In a 500 ml round bottom flask, add ligand (11.18 g, 16.89 mmol), silver oxide (7.83 g, 33.78 mmol), (PPh ₃ ) ₃ OsCl ₂ (8.85 g, 8.44 mmol) And anhydrous DMF (300 ml). The reaction was heated to 150 ° C under nitrogen for 1 hour. The reaction mixture was filtered and the precipitate was washed with dichloromethane. The filtrate was concentrated, and to accept column chromatography (SiO _2, triethylamine pretreated in hexanes of 25% CH ₂ Cl ₂ in hexanes to of 50% CH ₂ Cl _2), to give es -9 (9l0 mg, 22%).

The compounds es-l, es-2, es-3, es-5 and es-6 were prepared by procedures analogous to those described above for the compounds es-4, es-7, es-8 and es-9 .

Example 7

Step 1: In a 500 ml 3-neck round bottom flask, add 1,3-diiodobenzene (10 g, 0.03 mol), tris-butyl carbazate (9.5 g, 0.072 mol), copper iodide. (0.57 g, 0.003 mol), 1,10- phenanthroline (2.16 g, 0.012 mol), cesium carbonate (27.36 g, 0.084 mol) and 400 ml of anhydrous DMF. The reaction mixture was heated to 80 ° C for 21 hours. The reaction mixture was diluted with 400 mL of water and extracted with dichloromethane. The organic layer was concentrated to dryness and purified eluting elut elut

Step 2: In a 500 mL 3-neck round bottom flask, aniline (25.4 g, 0.27 mol), triethylamine (27.69 g, 0.27 mol) and 370 ml of THF were added. 50 g of 2,4,6-trimethylbenzimid chloride was added dropwise at 0 °C. The reaction mixture was stirred overnight to yield 60 g of desired material.

Step 3: 2 g of decylamine from step 2 was dissolved in 7 ml of sulfite dichloride and heated at 70 ° C for 1 hour. The reaction mixture was concentrated to dryness and used in the next step.

Step 4: The ruthenium chloride imine from step 3 was dissolved in 5 ml of THF. A solution of Boc-protected hydrazine (1.41 g, 4.179 mmol) and triethylamine (1.16 mL, 8.36 mmol) was added dropwise at -10 °C. The reaction was then stirred at room temperature overnight. The reaction mixture was diluted with dichloromethane and washed with 0.1N EtOAc and sat. The organic layer was concentrated to dryness and taken to a column chromatography to give the desired compound (1.74 g).

Step 5: 1.74 g of the intermediate from step 4 was dissolved in 4N HCl in dioxane; the mixture was stirred at room temperature for 2.5 hours. The reaction mixture was then evaporated to dryness and used in the next step.

Step 6: The intermediate from Step 5 was combined with triethyl orthoformate (40 mL), HCl (2 mL) and a few drops of formic acid. The reaction mixture was heated to 80 ° C overnight. The reaction mixture was concentrated to 1/3 volume to induce precipitation. The reaction mixture was filtered to give the desired product (1.

Step 7: One gram of the intermediate from Step 6 was dissolved in dry methanol (40 mL) and 0.5N sodium methoxide solution (6.53 mL, 3.26 mmol) was added and the product (950 mg) was filtered.

Step 8: In a 500 ml 3-neck round bottom flask, add the ligand from step 7 (6.64 g, 9.98 mmol), Cl ₂ Os (PPh ₃ ) ₃ (2.6 g, 2.49 mmol) and M-xylene (150 ml). The reaction mixture was completely degassed and heated to reflux overnight. The reaction mixture was filtered and the filtrate was concentrated to dryness. The residue was subjected to column chromatography to yield 1.31 g of Os complex.

Example 8

OLEDs comprising a phosphorescent emissive material according to the present invention can be made according to the procedures described in U.S. Patent Application Serial No. 11/241,981, the entire disclosure of which is incorporated herein by reference.

The starting substrate was a glass substrate available from Colorado Concept Paint LLC, coated with indium tin oxide (ITO) at a thickness of 80 nm and having a sheet resistance of <25 ohms/square. All subsequent films were deposited by thermal evaporation at a pressure of <10 ^-6 Torr. Cathode contains 10 LiF, followed by 1,000 Al. All devices were immediately coated in a nitrogen glove box (<1 ppm H ₂ O and O ₂ ) with a glass cover, sealed with epoxy resin, and the moisture getter was incorporated into the interior of the package.

Prior to device fabrication, the substrate was cleaned in a soap solution by sonication, rinsed with deionized water, and boiled in isopropanol. After the cleaning procedure on the substrate is dried under N ₂ flow followed by O ₂ plasma and UV ozone treatment. The organic layer of the OLED is deposited on the substrate from the resistively heated alumina crucible by thermal evaporation at room temperature at a base pressure of <10 ^-6 Torr. The rate of the single component layer is controlled by an Inficon thickness monitor located close to the substrate. The specific rates for each material are shown in Table 1 below. With respect to the two component emissive layers, the rate of dopant is controlled by another crystal monitor located near the source of dopant evaporation. This other monitor is not exposed to the main flow of the subject.

The mCBP and HPT lines individually have the following structure:

The apparatus was fabricated and had the following device configurations as set forth in Table 2. The dopant concentration is expressed in % by weight.

The device characteristics for the device proposed in Table 2 are measured and are presented in Figures 5 to 69.

Example 9

In accordance with the present invention, an OLED comprising a phosphorescent emissive material from Example 7 (D356) is fabricated. The structure of this device is:

ITO (80 nm) / HIL4 (10 nm) / NPD (30 nm) / mCP: D356, 9% (30 nm) / mCP (X nm) / Alq ₃ (40 nm) / LiF / Al. See Figure 70. Device features for such devices are measured and are presented in Figures 71-75.

Although the present invention has been described with respect to the specific embodiments and preferred embodiments thereof, it is understood that the invention is not limited to the examples and specific embodiments. Therefore, the present invention as claimed is intended to include variations of the specific examples and preferred embodiments described herein, as those skilled in the art.

100. . . Device

115. . . anode

110. . . Substrate

120. . . Hole injection layer

125. . . Hole transport layer

130. . . Electronic blocking layer

135. . . Emissive layer

140. . . Hole blocking layer

145. . . Electron transport layer

150. . . Electron injection layer

155. . . The protective layer

160. . . cathode

162. . . First conductive layer

164. . . Second conductive layer

200. . . Device

210. . . Substrate

215. . . cathode

220. . . Emissive layer

225. . . Hole transport layer

230. . . anode

Figure 1 shows an organic light-emitting device having individual electron transport, hole transport and emission layers, and other layers.

Figure 2 shows an inverted organic light emitting device that does not have individual electron transport layers.

Figure 3 shows the electroluminescence spectra (expressed in arbitrary units) for devices DA, DB, DC and DD.

Figure 4 shows a plot of external quantum efficiency vs. luminosity for devices DA, DB, DC, and DD.

Figure 5 shows a plot of current density vs. voltage for devices DA, DB, DC, and DD.

Figure 6 shows a plot of normalized luminosity versus time for devices DA, DB and DD.

Figure 7 shows a plot of current density versus voltage for devices CA, CB, CC, CD, CE, and CF.

Figure 8 shows a plot of external quantum efficiency versus current density for devices CA, CB, CC, CD, CE, and CF.

Figure 9 shows the electroluminescence spectra for devices CA, CB, CC, CD, CE and CF.

Figure 10 shows the normalized luminosity versus time for devices CB, CD, CE, and CF.

Figure 11 shows a plot of current density versus voltage for devices CG, CH, CI, CJ, CK, and CL.

Figure 12 shows a plot of external quantum efficiency vs. current density for devices CG, CH, CI, CJ, CK, and CL.

Figure 13 shows the electroluminescence spectra for devices CG, CH, CI, CJ, CK and CL.

Figure 14 shows a plot of normalized luminosity versus time for devices CH and CK.

Figure 15 shows a plot of external quantum efficiency vs. current density for devices AAA and AAB.

Figure 16 shows the electroluminescence spectra for devices AAA and AAB.

Figure 17 shows a plot of current density versus voltage for devices AAA and AAB.

Figure 18 shows a plot of normalized luminosity versus time for devices AAA and AAB.

Figure 19 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A plot of current density versus voltage for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 20 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene An external quantum efficiency vs. luminosity diagram of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 21 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A graph of normalized luminosity versus time for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 22 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzo Electroluminescence spectrum of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 23 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A plot of current density versus voltage for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 24 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene An external quantum efficiency vs. luminosity diagram of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 25 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A graph of normalized luminosity versus time for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 26 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzo Electroluminescence spectrum of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 27 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A plot of current density versus voltage for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 28 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene An external quantum efficiency vs. luminosity diagram of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 29 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A graph of normalized luminosity versus time for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 30 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzo Electroluminescence spectrum of phenanthrene [5 nm] / Alq [45 nm] / LiF [0, 5 nm] / Al [100 nm].

Figure 31 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A plot of current density versus voltage for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 32 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11 - hexaphenylbenzene An external quantum efficiency vs. luminosity diagram of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 33 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzo Electroluminescence spectrum of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 34 shows the device: CuPc [10 nm] / NPD [30 nm] / CBP: es-5, 10% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A graph of normalized luminosity versus time for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 35 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / CBP [5 nm] / Alq [45 nm] / LiF [ A plot of current density vs. voltage for 0.5 nm]/Al [100 nm].

Figure 36 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / CBP [5 nm] / Alq [45 nm] / LiF [ A plot of external quantum efficiency versus luminosity for 0.5 nm]/Al [100 nm].

Figure 37 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / CBP [5 nm] / Alq [45 nm] / LiF [ A graph of normalized luminosity versus time for 0.5 nm]/Al [100 nm].

Figure 38 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / CBP [5 nm] / Alq [45 nm] / LiF [0.5 Electroluminescence spectrum of nanometers / Al [100 nm].

Figure 39 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A plot of current density versus voltage for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 40 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene An external quantum efficiency vs. luminosity diagram of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 41 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzene A graph of normalized luminosity versus time for phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 42 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / 2, 3, 6, 7, 10, 11-hexaphenylbenzo Electroluminescence spectrum of phenanthrene [5 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 nm].

Figure 43 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ A plot of current density versus voltage for 100 nm].

Figure L4 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ A plot of external quantum efficiency versus luminosity at 100 nm].

Figure 45 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ 100 nm] normalized luminosity versus time graph.

Figure 46 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 6% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 Electron luminescence spectrum of nanometer].

Figure 47 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ A plot of current density versus voltage for 100 nm].

Figure 48 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ A plot of external quantum efficiency versus luminosity at 100 nm].

Figure 49 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [ 100 nm] normalized luminosity versus time graph.

Figure 50 shows the device: HIL4 [10 nm] / NPD [30 nm] / CBP: es-5, 15% [30 nm] / Alq [45 nm] / LiF [0.5 nm] / Al [100 Electron luminescence spectrum of nanometer].

Figure 51 shows a plot of external quantum efficiency versus current density for devices A, B, C, D, F, and F.

Figure 52 shows a plot of current density versus voltage for devices A, B, C, D, E, and F.

Figure 53 shows the electroluminescence spectra of devices A, B, C, D, E and F.

Figure 54 shows a plot of normalized luminosity versus time for devices A, B, C, D, E, and F.

Figure 55 shows a plot of current density vs. voltage for devices AA, AB, AC, AD, AE, and AF.

Figure 56 shows a plot of external quantum efficiency versus current density for devices AA, AB, AC, AD, AE, and AF.

Figure 57 shows the electroluminescence spectra of the devices AA, AB, AC, AD, AE and AF.

Figure 58 shows a plot of normalized luminosity versus time for devices AA and AB.

Figure 59 shows a plot of current density versus voltage for devices AG, AH, AI, AJ, and AK.

Figure 60 shows a graph of external quantum efficiency versus current density for devices AG, AH, AI, AJ, and AK.

Figure 61 shows the electroluminescence spectra of the devices AG, AH, AI, AJ and AK.

Figure 62 shows a plot of external quantum efficiency versus current density for devices BA, BB, BC, and BD.

Figure 63 shows a plot of current density vs. voltage for devices BA, BB, BC and BD.

Figure 64 shows a plot of external quantum efficiency versus current density for devices BE, BF, BG, and BH.

Figure 65 shows a plot of current density vs. voltage for devices BE, BF, BG, and BH.

Figure 66 shows the electroluminescence spectra of the devices BA, BB, BC, BD, BE, BF, BG and BH.

Figure 67 shows a plot of normalized luminosity versus time for devices BC, BF, BE, and BG.

Figure 68 shows the structures of the compounds es-1, es-2, es-3 and es-4.

Figure 69 shows the structures of the compounds es-5, es-6, es-7 and es-8.

Figure 70 shows the structure of the device relating to Example 9.

Figure 71 shows a graph of external quantum efficiency vs. luminosity for the device of Example 9.

Figure 72 shows a graph of power efficiency (Lm/W) versus luminosity for the device of Example 9.

Figure 73 shows a plot of luminosity versus voltage for the device of Example 9.

Figure 74 shows a plot of EL intensity versus wavelength for the device of Example 9.

Figure 75 shows a graph of device lifetime (normalized luminosity vs. time) at 1000 nits for the Example 9 device.

100. . . Device

115. . . anode

110. . . Substrate

120. . . Hole injection layer

125. . . Hole transport layer

130. . . Electronic blocking layer

135. . . Emissive layer

140. . . Hole blocking layer

145. . . Electron transport layer

150. . . Electron injection layer

155. . . The protective layer

160. . . cathode

162. . . First conductive layer

164. . . Second conductive layer

Claims (6)

An organic light-emitting device comprising: an anode; a cathode; and a phosphorescent emitting region disposed between the anode and the cathode, wherein the emitting region comprises an emitting material having the formula IV: Wherein: M is a second or third column transition metal; a broken line indicates a double bond as the case exists; L is an auxiliary ligand; X2 is selected from CR ² or N; and R ² is selected from H, an alkyl group, an alkenyl group , alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R′, SOR′, SO ₃ R′, Si(R”) ₃ , halo, aryl and heteroaryl; R ⁵ is selected from H, alkyl, alkenyl, alkynyl, aryl Alkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ⁷ is selected from H, alkyl, alkenyl, alkynyl, aralkyl, O- R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR' , SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ¹² is selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and C(O)R'; ¹³ and R ¹⁴ are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR ', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and a heteroaryl group; additionally or alternatively, R ¹³ and R ¹⁴ form a fused 5- or 6-membered cyclic group, wherein the fused cyclic group is optionally substituted with one or more substituents, substituents Selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si (R") ₃ , halo, aryl and heteroaryl; R ²² is selected from alkyl, aryl , aralkyl, cycloalkyl and C(O)R'; R ²³ and R ²⁴ are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si ( R ") _3, halo, aryl and heteroaryl; Additionally or alternatively, R ²³ and R ²⁴ form a fused-based 5- or 6-membered cyclic group, wherein the cyclic group fused system optionally Substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C ( O) OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl Each R' is independently selected from H, alkane a base, an alkenyl group, an alkynyl group, an arylalkyl group, an aryl group and a heteroaryl group; each R" is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aralkyl; n is 1 or 2; and m is 0-3, wherein when n is 1, m is 1-3, and when n is 2, m is 0. The device of claim 1, wherein M is Os. The device of claim 1, wherein the emission material is of the following formula: a compound having the formula IV: Wherein: M is a second or third column transition metal; a broken line indicates a double bond as the case exists; L is an auxiliary ligand; X ² is selected from CR ² or N; and R ² is selected from H, an alkyl group, an alkene Base, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R′, SOR′, SO ₃ R′, Si(R”) ₃ , halo, aryl and heteroaryl; R ⁵ is selected from H, alkyl, alkenyl, alkynyl, Aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ⁷ is selected from H, alkyl, alkenyl, alkynyl, aralkyl, O -R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR ', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl; R ¹² is selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and C(O)R'; R ¹³ and R ¹⁴ are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O) OR ', C (O) NR ' 2, CN, CF 3, NO 2, SO 2 R ', SOR', SO 3 R ', Si (R ") 3, halo, aryl Heteroaryl; Additionally or alternatively, R ¹³ and R ¹⁴ form a fused-based 5- or 6-membered cyclic group, wherein the cyclic group fused system optionally substituted with one or more substituents, the substituents Selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si (R") ₃ , halo, aryl and heteroaryl; R ²² is selected from alkyl, aryl , aralkyl, cycloalkyl and C(O)R'; R ²³ and R ²⁴ are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C(O)OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si ( R ") _3, halo, aryl and heteroaryl; Additionally or alternatively, R ²³ and R ²⁴ form a fused-based 5- or 6-membered cyclic group, wherein the cyclic group fused system optionally Substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ₂ , SR', C(O)R', C ( O) OR', C(O)NR' ₂ , CN, CF ₃ , NO ₂ , SO ₂ R', SOR', SO ₃ R', Si(R") ₃ , halo, aryl and heteroaryl Each R' is independently selected from H, Group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, and heteroaryl; each R "is independently selected lines H, an alkyl group, alkenyl group, alkynyl group and aralkyl group; n is 1 or 2; and m is 0-3, wherein when n is 1, m is 1-3, and when n is 2, m is 0. The compound of claim 4, wherein M is Os. The compound of claim 4, which has the formula: